Cationically polymerizable macromolecular monomers and graft copolymers therefrom

ABSTRACT

The method and production of macromolecular monomers from cationically polymerizable monomers and vinyl-substituted hydrocarbon halides is disclosed. These cationically polymerizable monomers may react in the presence of a catalyst with the hydrocarbon halide to produce a macromer retaining a polymerizable headgroup. This compound may be used in a variety of copolymerization processes with a variety of copolymerizable monomers to form graft copolymers.

TECHNICAL FIELD

This invention relates to the production of macromolecular monomers fromcationically polymerizable monomers and vinyl-substituted hydrocarbonhalides, which may be used in copolymerization with copolymerizablemonomers to form a graft copolymer.

BACKGROUND ART

Macromolecules carrying a readily polymerizable headgroup on apolymerization-inactive chain have been demonstrated to yield valuablemacromolecular monomers. These macromolecular monomers, abbreviated inthe art to macromers, may copolymerize with conventional monomers toproduce graft copolymers. This method of macromer copolymerization hasbeen described by the following reaction: ##STR1##

To the knowledge of the inventors, the production of macromers by directone-step synthesis has been mainly through use of an anionic mechanismsuch as that disclosed by U.S. Pat. Nos. 3,989,768; 3,879,494;3,786,116; and 3,832,423. Various disclosures in the art are found inVolume 101 Makromolecular Chemistry 104 (1967), Journal of PaintTechnology 46, 596, 16 (1974), Journal of Applied Polymer Science, 14,167 (1970), and Polymer Bulletin 1, 575-580. (1979).

The production of macromers using anionic techniques neglects manymonomers which can be synthesized by carbocationic techniques.Therefore, the need exists for a reaction system to synthesize macromersfrom cationically polymerizable monomers, useful in macromercopolymerization to form graft copolymers.

DISCLOSURE OF INVENTION

Therefore, it is an object of the invention to provide a cationicallyprepared macromolecular monomer, macromer.

It is another object of the invention to provide a cationically preparedmonomer, as above, having polymerizable headgroups.

It is yet another object of the invention to provide a cationicallyprepared macromer having polymerizable headgroups produced from thereaction of a vinyl-substituted hydrocarbon halide and a cationicallypolymerizable monomer.

Still another object of the invention is to provide a graft copolymerproduced from a copolymerizable monomer and the cationically preparedmacromer described above.

Yet another object of the invention is to provide a graft copolymer asabove, wherein any copolymerizable monomer may copolymerize with thecationically prepared macromer at the polymerizable headgroups.

Yet another object of the invention is to provide a method for theproduction of a cationically prepared macromer having polymerizableheadgroups.

It is yet another object of the invention to provide a method for theproduction of a graft copolymer produced from the reaction of acationically prepared macromer and a copolymerizable monomer.

These and other objects of the invention, which will become moreapparent as the detailed description of the best mode for carrying outthe invention proceeds, are achieved by a composition of matter,comprising: a cationically prepared macromolecular monomer.

The objects of the invention are also achieved by a composition ofmatter, comprising: poly (X--g--Y) where X is a copolymerizable monomerand where Y is a cationically prepared macromolecular monomer.

The objects of the invention are also achieved by a method for theproduction of a cationically polymerized macromer comprising: chargingfrom about 5.0 moles to about 1×10⁻⁵ moles of a vinyl-substitutedhydrocarbon halide into a vessel containing about 1 mole of acationically polymerizable monomer and about 1.0 moles to about 1.0×10⁻⁵moles of a cationic polymerizing catalyst, and

reacting said hydrocarbon halide and said monomer in the presence ofsaid catalyst at a temperature from about -100 degree C to about 30degrees C and under N₂ atmosphere to form a cationically preparedmacromolecular monomer.

The objects are also achieved by a method for the production of a graftcopolymer by macromer copolymerization, comprising: charging from about5.0×10⁻² moles to about 5.0×10⁻⁷ moles of a cationically preparedmacromolecular monomer into a vessel containing about 1 mole of acopolymerizable monomer and about 0.1 moles to about 1.0×10⁻⁶ moles of acatalyst, and

copolymerizing said cationically prepared macromolecular monomer andsaid copolymerizable monomer at a temperature from about -20 degrees Cto about 180 degrees C to form a graft copolymer of the formula poly(X--g--Y) where X is the copolymerizable monomer and where Y is thecationically prepared macromolecular monomer.

BRIEF DESCRIPTION OF DRAWINGS

For an understanding of the synthesis of the cationically preparedmacromer and the graft copolymers therefrom, reference is made to thefollowing figures, wherein:

FIG. 1 is a graph demonstrating the conversion of the macromer synthesisplotted against time;

FIG. 2 is a graph demonstrating a comparison of ultraviolet-visiblespectral data, comparing the macromer of the present invention with amethyl-substituted sytrene to determine headgroup concentration;

FIG. 3 is a compilation of three nuclear-magnetic resonance spectrademonstrating the formation of the graft copolymer of the presentinvention, having a backbone of one polymer and branch of the secondpolymer; and

FIG. 4 is a graph of various DSC scans demonstrating a plurality ofglass-transition-temperature data for the graft copolymers of thepresent invention in comparison with the free-radically polymerizablemonomers and the cationically prepared monomer.

BEST MODE FOR CARRYING OUT THE INVENTION

Macromer copolymerization is defined to by the polymerization of amacromer with a copolymerizable monomer. The macromer must have acopolymerizable headgroup for polymerization. This reaction generates arandom copolymer comprising a conventionally copolymerizable monomer andthe macromer, which, by the incorporation of the latter, introduces abranch to the backbone resulting in the graft copolymer. Thus macromercopolymerization differs from graft copolymerization in the sequence offormation of the backbone relative to the formation of the graft unit.

The limitation of macromer copolymerization to those monomers which areanionically polymerizable places severe restrictions upon cationicallypolymerizable monomers which would produce desirable graft copolymers.Therefore, a key feature of this invention is to synthesize the macromerfrom cationically polymerizable monomers carrying unreactedpolymerizable headgroups for subsequent copolymerization.

The cationically polymerizable monomers of the present invention may beany monomer capable of cationic polymerization. As such, cationicallypolymerizable monomers may polymerize to form a unit later identified asthe branch of the graft copolymer of the present invention. Examples ofcationically polymerizable monomers include isobutylene, styrene,α-methylstyrene, indene, tetrahydrofuran, oxethane, isobutyl vinylether.

To generate a macromer having a polymerizable headgroup which survivesthe polymerization of the cationically polymerizable monomer, it isnecessary to use a vinyl or α-substituted vinyl hydrocarbon carrying atertiary, benzylic, or allylic halide, hereinafter calledvinyl-substituted hydrocarbon halide. The hydrocarbon may be aliphatic,aromatic, or combinations thereof, having from 1 to 18 carbon atoms. Atone end of this hydrocarbon must be a vinyl or α-substituted vinylgroup. At another end of the hydrocarbon must be a group having atertiary, benzylic, or allylic halide. Examples of the vinyl-substitutedhydrocarbon halide of the present invention are vinyl benzyl halide andan allylic halide having the following formula: ##STR2## where R is ahydrocarbon having from 1-18 carbon atoms, where R' is either H or ahydrocarbon having from 1-18 carbon atoms, where R and R', may be thesame and where X=F, Cl, BR, or I.

The reaction of the vinyl-substituted hydrocarbon halide and thecationically polymerizable monomer can be initiated by a variety ofLewis acid catalysts suited for cationic polymerization. These catalystsmay be any Friedel-Crafts acids as described in Friedel-Crafts andRelated Reactions Vol. 1, Interscience, 1963. Examples aretrimethylaluminum, triethylaluminum, diethylaluminum chloride,ethylaluminum dichloride, diisobutylaluminum chloride, borontrichloride, and ethylaluminum sesquihalide.

In addition to Lewis acid catalysts, certain heavy metal salts ofnon-nucleophilic counter anions of the formula ST may be used, where Smay be a heavy metal such as Ag, Hg, Cd, or Pb, and where T may benon-nucleophilic counter anion such as PCl₆ ⁻, PF₆ ⁻, SbF₆ ⁻, SbCl₆ ⁻,BF₄ ⁻, ClO₄ ⁻, and AsF₅ ⁻.

The reaction of the vinyl-substituted hydrocarbon halide and thecationically polymerizable monomer in the presence of the cationicpolymerizing catalyst requires the following reaction concentration:from about 5.0 to about 1.0×10⁻⁵ moles of vinyl-substituted hydrocarbonhalide per mole of cationically polymerizable catalysts exists fromabout 1.0 moles to about 1.0×10⁻⁵ moles per moles of cationicallypolymerization monomer.

Within these ranges of concentrations, it is desirable to have aconcentration of vinyl-substituted hydrocarbon halide from 3.0×10⁻²moles to about 5.0×10⁻⁴ moles per mole of cationically polymerizablemonomer. Further, it is desirable to have a concentration of cationicpolymerization catalyst from about 0.5 moles to about 1.0×10⁻⁴ moles permole of cationically polymerizable monomer.

It is preferred to have from about 0.1 moles to about 1.0×10⁻⁴ moles ofvinyl-substituted hydrocarbon halide per mole of cationic polymerizablemonomer. Further, it is preferred to have from about 0.2 moles to about1.0×10⁻³ moles of cationic polymerization catalyst per mole ofcationically polymerizable monomer. Optimally, the concentration ofvinyl-substituted hydrocarbon halide is from about 0.01 moles to about0.005 moles per mole of cationic polymerizable monomer. Optimally, theconcentration of the cationic polymerization catalyst is from about 0.1to about 0.2 moles per mole of cationic polymerizable monomer.

The above ranges of concentration do not reflect the solvent system intowhich the hydrocarbon, the monomer, and the catalyst are placed. Thesolvent system may desirably be toluene, dichloromethane, benzene,1,2-dichloroethane, n-heptane, chlorobenzene, CH₂ Cl₂, allyl chloride,methyl chloride, and combinations thereof. Preferably, the solventsystem is from about 100 percent to about 0 percent of CH₃ Cl/from about0 percent to about 50 percent n-heptane. Preferably, the solvent systemis about 80 percent CH₃ Cl/20 percent n-heptane. Desirably, the reactionvessel is closed and maintains a pure nitrogen (N₂) atmosphere. Thereaction occurs at a temperature from about +30 degrees C to about -100degrees C and preferably occurs at -60 degrees C.

Of the cationically polymerizable monomers, which include anycationically polymerizable monomer known to those skilled in the art,isobutylene is preferred. Of the vinyl-substituted hydrocarbon halides,including any hydrocarbon halides known to those skilled in the art,vinyl benzyl chloride is preferred. In alternative nomenclature, vinylbenzyl chloride is chloromethylstyrene with the substitution occuringpreferably either at the meta or the para position. Of the cationicpolymerization catalysts listed, trimethylaluminum is preferred. It hasbeen found that moisture increases the efficiency. The water may existin a concentration from about 0.0001 moles to 0.01 moles per mole ofcatalyst added.

In the preferred concentration, using the preferred reactants, under thepreferred conditions, a cationically prepared macromer was produced.This cationically prepared macromer is synthesized according to thefollowing reaction process: ##STR3##

As may be seen by the above chart, vinyl benzyl chloride (A) is ionizedby the catalyst to form vinyl benzyl cation (B). This cation then reactswith isobutylene (C) to form poly(isobutenyl styrene) macromer cation(D). Methylation of the cationic site completes the synthesis of thecationically polymerized macromer (E).

It has been found that the rate of polymerization is dependent upon theconcentration of the cationically polymerizable monomer, that is to say,the reaction kinetics for the homopolymerization of isobutylene.Therefore, it has been found that about 100 moles of isobutylene permole of vinyl benzyl chloride will permit homopolymerization of theisobutylene to form the macromer (E).

Crucial to the formation of the macromer (E) is the retention of thepolymerizable vinyl headgroup, which serves for random copolymerizationwith the copolymerization monomer to form the graft copolymer. At anystage during the reaction mechanism described above, it may be possibleto have deleterious side reactions which inhibit the formation of themacromer having the vinyl headgroup. Side reactions known are thefollowing ##STR4##

Side reaction (1) indicates the copolymerization of thevinyl-substituted hydrocarbon halide. This undesirable copolymerizationremoves the vinyl headgroup of that compound from subsequent desirablecopolymerization. As seen in reaction (1), not only does thiscopolymerization remove the hydrocarbon halide from macromer formationbut also encumbers the graft by providing an additional undesirable sidechain on the graft, such as that seen in compound (F). Further, compound(F), having a reactive halide site may initiate homopolymerization ofisobutylene along the chain to form compound (G), further encumberingthe graft, as seen in side reaction (2). Otherwise methylation at thehalide site forms compound (H), as seen in reaction (3).

Compound (G) may also be produced by the copolymerization of twomacromers. As above, this eliminates the availability of the vinylheadgroup for subsequent desirable copolymerization and also creates abranched graft copolymer. As seen in side reaction (4), compound (G) isthe same as that produced in reaction (2), except that thehomopolymerization of isobutylene has previously occurred.

The macromer is characterized by determining the percentage of vinylheadgroups surviving cationic polymerization by ultraviolet-visiblespectral analysis. This spectral analysis offers a comparison of thepoly(isobutenyl styrene) in comparison with a known aromatic hydrocarbonhaving a vinyl headgroup, to wit: ortho, meta, or para methylstyrene.Survival of every vinyl headgroup in the macromer would be indicated by100 percent retention of vinyl headgroups.

The poly(isobutenyl styrene) was produced according to the preferredconcentrations in the preferred solvent concentrations in the preferredatmospheric and temperature conditions. Comparative data utilizing theequation: A=bc provides a direct percentage companion for the followingequation: ##EQU1## The numerical values for the above equation arecomputed by measuring the absorbance of the macromer as seen in FIG. 2,calculating the path length in centimeters, determining the density ofthe macromer, and determining the number average molecular weight of themacromer. The extinction coefficient for the methyl-substituted styrenewas determined from known values for an absorbance maximum at 250 nm.This determination indicates that 84 percent of the vinyl headgroupssurvived the polymerization of the vinyl-substituted hydrocarbon halidewith the cationically polymerizable monomer. The remaining 16% of thevinyl headgroups were consumed by one of the undesirable side reactionsindicated above. The calculation of Mn was made using GPC equipment, andthe molecular weight was well within the desired range from 5,000 to100,000 suitable for macromolecular monomers. Three otherpolymerizations using the same concentrations and conditions yielded apercentage efficiency from about 83 to about 90 percent retention ofvinyl headgroups.

Following the formation of the cationically prepared macromolecularmonomer retaining polymerizable headgroups, it is desirable topolymerize that macromer with a copolymerizable monomer to form a graftcopolymer. The copolymerizable monomer may be any monomer capable ofcopolymerization with the polymerizable headgroup of the macromer, suchas free-radical polymerizable monomers, cationic polymerizable monomers,anionic polymerizable monomers, and polymerizable monomers, bycoordination mechanisms.

The free-radical polymerizable monomer may be any free-radicalpolymerizable monomer known to those skilled in the art, including butylacrylate, methyl methacrylate, acrylonitrile, styrene, vinyl acetate,vinyl chloride, ethyl acetate, vinylidene chloride, and combinationsthereof. Of the free-radical polymerizable monomers, it is desirable touse butyl acrylate or methyl methacrylate.

The cationic polymerizable monomers may be any cationic polymerizablemonomer known to those skilled in the art, including isobutylene,α-methylstyrene, isobutyl vinyl ether, indene, tetrahydrofuran,oxethane, styrene, various substituted sytrenes and combinationsthereof. Of the cationic polymerizable monomers, it is desirable to usesytrene or α-methylstyrene.

The anionic polymerizable monomers may be any anionic polymerizablemonomer known to those skilled in the art, including styrene, butadiene,isoprene, α-methylstyrene, and combinations thereof. Of the anionicpolymerizable monomers, it is desirable to use styrene orα-methylstyrene.

The coordination polymerizable monomers may be any polymerizablemonomers reacting by coordination or Ziegler-Natta mechanisms known tothose skilled in the art, including ethylene, propylene, 1-butene,butadiene, oxiranes such as ethylene oxide, propylene oxide, and thelike, or combinations thereof. Of the coordination polymerizablemonomers, it is desirable to use ethylene or propylene.

The copolymerization of the macromer with this free-radicalpolymerizable monomer requires a free-radical catalyst such asazobisisobutyronitrile (AIBN), peroxides such as benzoyl peroxide,tert-butyl hydroperoxide, tert-butyl peroctoate, as well as variousoxidation-reduction radical initiators such as Fenton's reagent (H₂ O₂+Fe⁺²) and the like. Catalysts for the copolymerization of the macromerand a cationic polymerizable monomer are Lewis acid catalysts and heavymetal salts of non-nucleophilic counter anions such as described abovefor the preparation of the macromer. Catalysts for the copolymerizationof the macromer and an anionic polymerizable monomer are RLi, R'Na whereR is butyl and secondary butyl and where R' is naphthalene, as well asalkali metals such as Li, Na, and K. Catalysts for the copolymerizationof the macromer and a coordination polymerizable monomer are anycoordination catalyst described in Coordination Polymerization Ed. by J.C. W. Chien, Academic Press, Inc. 1975, such as TiCl₄ /Et₂ AlCl.

The reaction may occur with the macromer and the copolymerizable monomerin a suitable organic solvent in which both are soluable, such astoluene, benzene and the like. The atmospheric conditions are an inertatmosphere free of oxygen. The temperature of copolymerization is fromabout -20 degrees C to about 180 degrees C, depending upon thecopolymerization reaction mechanism, as is well known to those skilledin the art. For free-radical copolymerization, 50 degrees C isdesirable.

The concentration of the macromer may range from about 5.0×10⁻² moles toabout 5.0×10⁻⁷ moles per mole of copolymerizable monomer. Desirably, therange of concentration is from about 1.0×10⁻⁵ to about 1.0×10⁻⁶ molesper mole of copolymerizable monomer. Preferably, the macromerconcentration is about 5.0×10⁻⁶ moles per mole of copolymerizablemonomer.

The concentration of catalyst is from about 1.0×10⁻⁶ moles to about 0.1moles per mole of copolymerizable monomer. Desirably, the catalystconcentration is from about 1.0×10⁻⁴ to about 0.1 moles per mole ofcopolymerizable monomer, when free-radical copolymerizable monomers areused. Desirably, the cationic copolymerization catalyst concentration isfrom about 1×10⁻⁵ to about 0.2 moles per mole of copolymerizaitoncatalyst concentration is from about 1×10⁻⁶ to about 1×10⁻² moles permole of copolymerizable monomer. Desirably, the coordinationcopolymerization catalyst concentration is from about 1×10⁻⁶ to about5×10⁻² moles per mole of copolymerizable monomer. Desirably, themacromer, monomer, and catalyst are dissolved in about 9.0 moles ofsolvent per monomer. Preferably when free-radical polymerizable monomersare used the macromer, monomer, and catalyst are dissolved in about 1.85moles of toluene per mole of free-radical polymerization monomer.

When the macromer is produced according to the above methods, andpoly(isobutenylstyrene) is synthesized, this may be reacted with afree-radical polymerizable monomer such as butyl acrylate or methylmethacrylate to form the following copolymers:poly(butylacrylate-g-isobutylene) or poly(methylmethacrylate-g-isobutylene). Generally, the graft copolymer producedaccording to this invention is poly(free-radical polymerizablemonomer-g-cationically prepared macromer).

The synthesis of the graft copolymer of the present invention may bedemonstrated by a comparison of nuclear magnetic resonance graphs suchas those seen in FIG. 3. For a graft copolymer prepared from butylacrylate and poly(isobutenylstyrene), the nuclear magnetic resonance ofthe graft copolymer should reflect the combination of the polymerscomprising the backbone and the graft. Examining FIG. 3, it is apparentthat the combination of the H⁺¹ NMR for poly (butylacrylate),poly(isobutylene), and poly(butylacrylate-g-isobutylene) indicates theexistence of a polybutyl acrylate backbone and a polyisobutylene graft.Therefore, the production of the preferred graft copolymer of thepresent invention has been identified by NMR studies to isolate thebackbone polymer and the graft polymer, as seen in FIG. 3.

As described above, another cationically polymerizable monomer istetrahydrofuran. In the presence of a catalyst such as AgPCl₆ ⁻, nodiscernible polymer is produced. However, in the presence of thatcatalyst and a vinyl-substituted hydrocarbon halide such as vinyl benzylchloride, a macromolecular monomer containing tetrahydrofuran wasproduced, having a yield of about 86 percent. Because tetrahydrofuranrequires cationic initiation, the vinyl benzyl chloride provides thevinyl benzyl cation upon ionization by the AgPl₆ ⁻. Upon reaction of thetetrahydrofuran with the vinyl benzyl cation, thepoly(tetrahydrofurylstyrene) is produced.

INDUSTRIAL APPLICABILITY

The production of a graft copolymer utilizing macromer copolymerizationprovides a random copolymerization of the free-radical polymerizablemonomer with the macromer having cationically polymerizable monomerscontained therein. Depending upon the monomers selected, the graftcopolymer may be a thermoplastic elastomer having two separate glasstransition temperatures, one in the glassy phase and another in therubbery phase. Otherwise, the glass transition temperatures may be bothin the rubbery phase. Depending upon the monomers selected, a variety ofgraft copolymers for specific industrial functions may be produced.These polymers are useful for impact resistant theremoplastics, blendingagents, adhesives, and other purposes.

Employing the cationic polymerizing catalyst and the cationic macromerpreparation process, monomers previously excluded from macromersynthesis may now be formed for the above uses. These cationictechniques permit any cationically polymerizable monomer to synthesizewith any vinyl-substituted hydrocarbon halide to form a cationicallyprepared macromer, which in turn may polymerize with any copolymerizablemonomer to form a wide variety of graft copolymers.

In the preferred embodiment, the snythesis of poly(isobutenylstyrene)macromer with either butyl acrylate or methyl methacrylate may show thedistinct glass transition temperatures vital for proper blending of thegraft copolymer. Referring to FIG. 4, a graph showing DSC scans, thecomparison of the glass transition temperatures for the graft copolymersof the present invention with their constituent groups may be seen. Line3 is the DSC scan for poly(isobutenylstyrene) macromer, while scan 2 andscan 4 are for poly(butylacrylate) and poly(methyl methacrylate),respectively. The DSC scan of one graft copolymer, poly(butylacrylate-g-isobutylene) is shown in line 1, while the DSC scan forpoly(methyl methacrylate-g-isobutylene) is shown on line 5. The presenceof two distinct glass transition temperatures for these graft copolymersof the present invention demonstrate the industrial applicability of thegraft copolymers, in applications where toughened or impact resistantthermoplastics are used. It is seen that poly(butylacrylate-g-isobutylene) has both glass transition temperature in therubbery range, which renders that graft copolymer useful for blendingpoly(butyl acrylate) rubber with butyl rubber. In contrast, the glasstransition temperatures of poly(methyl methacrylate-g-isobutylene) arewidely divergent. This renders the graft copolymer particularly usefulas impact resistant poly(methyl methacrylate).

While in accordance with the patent statutes, the best mode for carryingout the invention has been provided, it is to be understood that theinvention is not limited thereto or thereby. Consequently, for anunderstanding of the scope of the invention, reference is had to thefollowing claims.

What is claimed is:
 1. A macromolecular monomer comprising the reactionproduct of a cationically polymerizable monomer, said monomer beingisobutylene, and a vinyl substituted hydrocarbon halide having theformula ##STR5## where R' is a hydrocarbon having from 1 to 18 carbonatoms, and where X is selected from the group consisting of F, Cl, Br,and I,in said reaction the amount of said vinyl substituted hydrocarbonhalide is from about 5.0 moles to about 1.0×10⁻⁵ moles per mole of saidisobutylene monomer, and wherein said macromolecular monomer haspolymerizable head groups, said polymerizable head groups being vinyl orsubstituted vinyl groups.
 2. A macromolecular monomer, according toclaim 1, wherein said vinyl-substituted hydrocarbon halide and saidisobutylene monomer react in the presence of a cationic polymerizationcatalyst, said catalysts being a Lewis acid catalyst, said catalystpresent in a concentration from about 1.0 moles to about 1.0×10⁻⁵ molesper mole of said isobutylene monomer.
 3. A macromolecular monomer,according to claim 2, wherein reaction occurs at from about +30 degreesC. to about -100 degrees C, wherein said catalyst is selected from thegroup consisting of trimethylaluminum, triethylaluminum, diethylaluminumchloride, ethylaluminum dichloride, ethylaluminum sesquihalide,diisobutylaluminum chloride, boron trichloride and combinations thereof.4. A macromolecular monomer, according to claim 3, wherein saidhydrocarbon halide is vinyl benzyl chloride.
 5. A macromolecular monomeraccording to claim 4, wherein said reaction occurs in a nitrogenatmosphere.
 6. A macromolecular monomer according to claim 5, includingcarrying out said reaction in the presence of from about 0.0001 to about0.01 moles of water per mole of said catalyst.
 7. A macromolecularmonomer according to claim 6, wherein said catalyst istrimethylaluminum.
 8. A macromolecular monomer according to claim 3, 4,5, 6, or 7, wherein the number average molecular weight ranges fromabout 5,000 to about 100,000.
 9. A macromolecular monomer according toclaim 3, 4, 5, 6, or 7, wherein in said reaction said vinyl-substitutedhydrocarbon halide had a concentration from about 3.0×10⁻² moles toabout 5.0×10⁻⁴ moles per mole of said cationically polymerizablemonomer, and wherein the amount of said catalyst is from about 0.2 toabout 1.0×10⁻³ moles per mole of said isobutylene monomer.
 10. Amacromolecular monomer, according to claim 3, 4, 5, 6, or 7, wherein insaid reaction said vinyl-substituted hydrocarbon halide has aconcentration of from about 0.01 to about 5×10⁻³ moles per mole of saidcationically polymerizable monomer, and wherein the amount of saidcatalyst is from about 0.1 to about 0.2 moles per mole of saidisobutylene monomer.
 11. A method for the production of a macromolecularmonomer produced by cationic polymerization, comprising:(a) chargingfrom about 5.0 moles to about 1×10⁻⁵ of a vinyl-substituted hydrocarbonhalide into a vessel containing about 1 mole of a cationicallypolymerizable monomer, said monomer being isobutylene, and about 1.0moles to about 1.0×10⁻⁵ moles of a cationic polymerizing catalyst, saidvinyl-substituted hydrocarbon halide having the formula ##STR6## whereinR' is hydrogen or a hydrocarbon having from 1 to 18 carbon atoms, and(b) reacting said hydrocarbon halide and said monomer in the presence ofsaid catalyst at a temperature from about -100° C. to about 30° C. andunder N₂ atmosphere to form a cationically prepared macromolecularmonomer having a molecular weight of from about 5,000 to about 100,000.12. A method according to claim 11,wherein said catalyst is selectedfrom the group consisting of trimethylaluminum, tiethylaluminum,trimethylaluminum and water, diethylaluminum chloride, ethylaluminumsesquihalide, ethylaluminum dichloride, diisobutylaluminum chloride,boron trichloride, and combinations thereof.
 13. A macromolecularmonomer, comprising: a compound having the formula ##STR7## wherein R'is hydrogen or a hydrocarbon having from 1 to 18 carbon atoms, andwherein said compound has a number average molecular weight of fromabout 5,000 to about 100,000.
 14. A macromolecular monomer according toclaim 13, wherein R' is hydrogen.
 15. A method according to claim 12,wherein said vinyl substituted hydrocarbon halide is vinyl benzylchloride.
 16. A method according to claim 15, including the step ofadding from about 0.0001 to about 0.01 moles of water per mole of saidcatalyst.
 17. A method according to claim 16, wherein said catalyst istrimethylaluminum.
 18. A method according to claim 15, 16, or 17,wherein the amount of said vinyl-substituted hydrocarbon halide rangesfrom about 3.0×10⁻² moles to about 5.0×10⁻⁴ moles per mole of saidisobutylene and wherein the amount of said catalysts ranges from about0.2 moles to about 1.0×10⁻³ moles per mole of said isobutylene monomer.